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Ligand control: The use of Pd complexes containing tBu3P or nitrogen-heterocyclic carbene (NHC) ligands almost completely prevents stereoisomerization, thereby permitting an efficient and selective methylation and higher alkylation of (Z)-2-bromo-1,3-dienes (see scheme, dba = trans,trans-dibenzylideneacetone).

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Theoretical studies on the overall catalytic cycle of isomerizing alkoxycarbonylation reveal the steric congestion around the diphosphine coordinated Pd-center as decisive for selectivity and productivity. The energy profile of isomerization is flat with diphosphines of variable steric bulk, but the preference for the formation of the linear Pd-alkyl species is more pronounced with sterically demanding diphosphines. CO insertion is feasible and reversible for all Pd-alkyl species studied and only little affected by the diphosphine. The overall rate-limiting step associated with the highest energetic barrier is methanolysis of the Pd-acyl species. Considering methanolysis of the linear Pd-acyl species, whose energetic barrier is lowest within all the Pd-acyl species studied, the barrier is calculated to be lower for more congesting diphosphines. Calculations indicate that energy differences of methanolysis of the linear versus branched Pd-acyls are more pronounced for more bulky diphosphines, due to involvement of different numbers of methanol molecules in the transition state. Experimental studies under pressure reactor conditions showed a faster conversion of shorter chain olefin substrates, but virtually no effect of the double bond position within the substrate. Compared to higher olefins, ethylene carbonylation under identical conditions is much faster, likely due not just to the occurrence of reactive linear acyls exclusively but also to an intrinsically favorable insertion reactivity of the olefin. The alcoholysis reaction is slowed down for higher alcohols, evidenced by pressure reactor and NMR studies. Multiple unsaturated fatty acids were observed to form a terminal Pd-allyl species upon reaction with the catalytically active Pd-hydride species. This process and further carbonylation are slow compared to isomerizing methoxycarbonylation of monounsaturated fatty acids, but selective.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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The comparison of the possibilities of Pd- and Cu-catalyzed amination reactions using fluorine-containing aryl bromides and iodides with oxadiamines to produce their N,N0-diaryl derivatives was carried out. The dependence of the reactivity of the aryl halides on the nature of the substituents and halogen atoms as well as on the structure of oxadiamines was investigated. It was found that the copper-catalyzed reactions were somewhat comparable with the palladium-mediated processes in the majority of cases, especially in the reactions with para-fluorine- and para-(trifluoromethyl)-substituted aryl halides, although the necessity to use aryl iodides in the Cu(I)-catalyzed amination was obvious. Pd catalysis was found inevitable for the successful amination of more sterically hindered ortho-(trifluoromethyl)aryl bromides.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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The side-by-side type palladium(I) complex (2) was synthesized either by the reaction among , (dba=dibenzylideneacetone), and (benzylthiomethyl)diphenylphosphine (btmp) or by the reaction of (1) and .The structure of 2 was established by a single-crystal X-ray diffraction study; the crystals were monoclinic, space group P21/c, with a=13.537(3), b=19.550(3), c=17.240(4) Angstroem, beta=114.59(2) deg, and Z=4; final R factor 0.049 for 5490 observed reflections.The structure showed that there is a metal-metal bond .Treatment of 2 with sodium iodide afforded the diiodo complex , whereas that with 4-methylpyridine (4-MePy) in the presence of AgClO4 gave 2.Moreover, 2 reacted with substituted acetylenes R=Ph, R’=H; R=CO2Me, R’=H; R=R’=CO2Me) to yield A-frame type complexes .All the complexes obtained in this study were characterized by means of elemental analysis, and IR and NMR spectroscopy.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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We describe the successful implementation of palladium-aryl oxidative addition complexes as stoichiometric reagents in carbonylation reactions with 11CO to produce structurally challenging, pharmaceutically relevant compounds. This method enables the first 11C-carbonyl labeling of an approved PET tracer, [11C]raclopride, for the dopamine D2/D3 receptor by carbonylation with excellent radiochemical purity and yield. Two other molecules, [11C]olaparib and [11C]JNJ 31020028, were efficiently labeled in this manner. The technique distinguishes itself from existing methods by the markedly improved purity profiles of the tracer molecules produced and provides access to complex structures in synthetically useful yields, hereby offering a viable alternative to other 11C-labeling strategies.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Novel aromatic amine compounds are provided. Light-emitting elements having high emission efficiency and high reliability are provided. Further, light-emitting devices and electronic devices using the light-emitting devices are provided. Specifically, an aromatic amine compound represented by the general formula (1), and light-emitting elements, light-emitting devices and electronic devices that are formed using the aromatic amine compound represented by the general formula (1) are provided. By using the aromatic amine compound represented by the general formula (1) for light-emitting elements, light-emitting devices and electronic devices, the light-emitting elements, light-emitting devices and electronic devices can have high emission efficiency.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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A new series of CB2-selective agonists containing a benzimidazole core is reported. Design, synthesis, SAR and pharmacokinetic data for selected compounds are described.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Palladacycles derived from l-tyrosine methyl ester, (S)-[Pd 2{C,N-C6H3CH2CH(CO 2Me)NH2-2,(OH)-4}2(mu-Br)2] (1a-Br), and homoveratrylamine, [Pd2{C,N-C6H 2CH2CH2NH2-6,(OMe) 2-3,4}2(mu-Br)2] (1b-Br), can be easily prepared in good yield by reacting Pd(OAc)2, the corresponding ammonium triflate, and NaBr. Under the same conditions, the reaction of Pd(OAc)2 with the free amine affords a low yield of the corresponding acetato complex 1a-OAc or 1b-OAc (the latter only detected in solution). In our hands, the previously reported palladation at the C2 position of homoveratrylamine with Pd(OAc)2 is not observed. Instead, a complex mixture is obtained, mainly containing [Pd(OAc)2{NH 2CH2CH2C6H3(OMe) 2-3,4}2] and minor amounts of 1b-OAc, which reacts with NaBr to afford a new mixture from which [PdBr2{NH2CH 2CH2C6H3(OMe)2-3,4} 2] can be isolated and characterized. These and other adducts can be isolated from Pd(OAc)2, homoveratrylamine, and various ligands (PPh3 and Br-). 6-Bromohomoveratrylamine reacts with Pd(dba)2 in the presence of tmeda to give the complex [Pd{C,N-C 6H2CH2CH2NH2-6,(OMe) 2-3,4}(tmeda)]Br. Reactions of complexes 1 with acetylacetonato or neutral (PR3) ligands give products resulting from substitution or bridge-splitting reactions. While 1a-Br reacts with XyNC (1:2 molar ratio) to give (S)-[Pd{C,N-C6H3CH2CH(CO 2Me)NH2-2,(OH)-4}Br(CNXy)], 1b-Br gives [Pd{C,N-C(=NXy)-C6H2CH2CH2NH 2-6,(OMe)2-3,4}Br(CNXy)]. (S)-7-Hydroxy-3- (methoxycarbonyl)-3,4-dihydroisoquinolin-1(2H)-one and 6,7-dimethoxy-3,4- dihydroisoquinolin-1(2H)-one (corydaldine) have been synthesized through the stoichiometric carbonylation of palladacycles 1a-Br and 1b-Br. The crystal structures of a solvento intermediate in the ortho-metalation reaction of the triflate derivative of l-tyrosine methyl ester and four other complexes have been determined by X-ray diffraction studies.

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Chapter 1 An introduction to palladium catalysis,
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Although carbonylation of aryl halides is widely applied in synthesis, heterogeneous catalysts for this transformation are scarce. In order to heterogeneously catalyze the amidocarbonylation of bromoarenes, a polymer-supported catalytic system was assembled from Pd(dba)2 and a polymer-bound diphosphine chelate, prepared via solid-phase synthesis from serinol. The system efficiently converts aryl bromides into carboxamides in a reaction with CO and aliphatic or aromatic amines. Comparison with other supported phosphine ligands demonstrated the superiority of the chelate diphosphine structure. Remarkably, partial complexation of the polymer-tethered ligating sites with Pd forms notably better catalytic systems than the full complexation. The reactivity pattern of the catalytic system points to the oxidative addition as the rate-determining step of the catalytic cycle.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Oxidative addition of different imidazolium cations to zerovalent group 10 metals, to afford heterocyclic carbene complexes, has been investigated by both density functional theory (DFT) and experimental studies. The theoretical analysis shows that addition of imidazoliums to Pt0 and Ni0 is more exothermic than to Pd0, and Ni0 is predicted to react with a much lower barrier than either Pt0 or Pd0 Strongly basic supporting ligands on the metal, as well as cis-chelating ligands, increase the exothermicity of the reaction and also lower the activation barrier. The addition of 2-H imidazoliums is easier and more exothermic than addition of 2-alkylimidazoliums, and a halo-imidazolium is expected to further lower the barrier to oxidative addition and increase the exothermicity. The DFT results show that all three of the metals should be able to oxidatively add imidazolium cations under appropriate conditions. Experimental studies confirmed that oxidative addition is possible, and a number of Pt- and Pd-carbene complexes were prepared via oxidative addition of imidazolium salts to M0 precursors. Most significantly, oxidative addition of 2-H azolium salts was found to readily occur, and the reaction of 1,3-dimethylimidazolium tetrafluoroborate with Pt(PPh3)2 and Pt(PCy3)2 affords [PtH(dmiy)(PPh3)2]BF4 (10) and [PtH(dmiy)(PCY3)2]BF4 (11), while reaction between 3,4-dimethylthiazolium tetrafluoroborate and Pt(PCy3)2 yields [PtH(dmty)(PCy3)2]BF4 (12) (dmiy = 1,3-dimethylimidazolin-2-ylidene, dmty = 3,4-dimethylthiazolin-2-ylidene). Addition of 2-iodo-1,3,4,5-tetramethylimidazolium tetrafluoroborate to Pt(PPh3)4 or Pd(dcype)(dba) yields [PtI(tmiy)(PPh3)2]BF4 (9) and [PdI(tmiy)(dcype)]BF4 (14), respectively (tmiy = 1,3,4,5-tetramethylimidazolin-2-ylidene, dcype = 1,3-bis(dicyclohexylphosphino)ethane)). X-ray crystal structures are reported for complexes 9 and 11 (cis and trans). These studies clearly show for the first time that oxidative addition of imidazolium and thiazolium cations is possible, and the results are discussed in terms of the ramifications for catalysis in imidazolium-based ionic liquids with both carbene-based and non-carbene-based complexes.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method